Monoazo dyestuff



Patented d June 2, 1925.

UNITED STATETES PATENT KARL THIESS, OF LINDLINGEN, NEAR HOEGHST-OBLiMAIN, GERMANY, ASSIGNOR TO FARBWERKE VORM. MEISTER LUCIUS 8a BBUNING, O]? HOEOHST-ON-MAIN, GEE- MANY, A CORPORATION OF GERlrfANY.

monoazo DYESTUFF.

No Drawing.

To all whom it may concern Be it known that I, KARL THIESS, a citizen of Germany residing at Lindlingen, near'Hoechst-on-Main, Germany, have invented certain new and useful Improvements.

in Monoazo Dyestuffs, of which the following is a specification.

Monoazodyestufl's from 'aininobenzaldehydes have hitherto been prepared only as 10 intermediate products for dyes, but they have not been particularly described. They have not yet been industrially used as such, because it has probably been supposed that the free aldehyde group in these dyestuffs has an injurious influence upon the fastness, stability, etc. of these monoazo-dyestuifs. For these reasons several attempts have been made to render the said aldehyde group innocuous, that is to say to cover it for instance by acting on it with phenylhydrazine-sulfonic acids or hydrazine (compare D. R. P. 85233, 90357, 91817).

I have now made the observation that by causing the diazo-cornpounds of m-amino- 26 benzaldehydes and their substitution prodnets and also compounds capable of splitting off m-aminobenzaldehyde to act upon pyrazolones or their hitherto unknown monoazo-dyestuifs are produced which have a free aldehyde group and give reactions characteristic thereof such as the formation of bisulfite compounds readily soluble in co-ldwater and'condensation with o-hydroxycarboxylic acids of the benzene and naphthalene series to leucotri arylmethane dyestufis; are readily soluble in hot water and dissolve in concentrated sulfuric acid with a yellowish-green 'toorange-yellow color; dye evenly. reddishyellow to greenish-yellow tints, and give in an acid bath dyeings of pure tints whichare very fast to light and alkalies and also pos sees a very great fastness to water and to washing which is much better than that of the hitherto known yellow equalizing dyestuffs of the pyrazolone series. I

The dyestuffs are represented by the following general formula:

CHOR-N:N-R

in which R stands for a benzene residue contains the aldehyde group in mposition substitution products,

Application filed Qctoner 8, 1923. Serial No. 667,409.

and R stands for arylpyrazolones, their derivatives and substitution products.

The following examples illustrate my invention a 1.) 36,8 kg. of 1n-aniinobenzaldehyde in the form of its hydrochloride are dissolved in water; this solutionhaving been diazotized in the known manner by a solution of 20,? kg. of sodium nitrite in 150 litres of" water at a temperature of 0-5 the mixture is coupled as usual with a solution of 85,2 kg. l-p-sulfophenyl-5-pyraZolone-3-carb0xylic acid in 600 litres of water and 40 kg. of calcinated SOCllUlll'CfilbOIlililG at 0-5". The formation of thedyestuif at once takes place and comes to an end after a short stirring at 2025. The dyestuff is entirely salted out by common salt; it dyes wool in an acid bath pure yellow tints with a green hue and is also extremely fit for wool-printing.

' The dyestuff has probably the following formula:&

t coon H 1 l C N l 4 1 Na u es N p scan .phenyl-pyrazolone-carboxylic acid by 76,2

kg. of l-p-sulphophenyl- -niethyl-5-pyrazolone, a dyestuff is obtained which dyes pure yellow tints and possessesa particular fastness to light.

4.) By replacing the 1-p-sulphophenyl-5- pyrazolone-3-carboxylic acid (Example 1) by 89,4 kg. 1(4 -sulpho2 -tolyl) 5-pyrazolone-3-carboxylic acid, a monoazodyestuflf is produced giving greenish-yellow tints.

5.) 46,2 kg. of 2-ehloro-fi-aminobenzaldehyde are diazotized as usual and combined to a monoazodyestuif in the known manner with 52,2 kg. l-phenyl-3-methyl-5-pyrazo lone dissolved in 600 litres of water and 36.

kg. caustic soda. The dried dyestuif when off aldehyde such as oximes, hvdrazoneslor' aldazines. Instead c t the pyrazolone der vatlves c ted nthe examples there may as well he used .e. halogen derivatives, such.

razolone or hydroxyderivatives such as 1(5 s1ilpho?31-earhoXy-2 -hydroxy) phenyl-i nethy-'l-fi-pyrazolone.

hyde are diazotizedas usual andcoupled at 0,5 with a soda alkaline solution of 76,2

kg. of l-p-sultophenyl-3-1nethyl-5 pyrazolone. The formation of thedyestufl-vsets in at once. The dyestutf afterbeing isolated by salting out forms whendry a 'reddishyellow powder which dyes wool inan. acid hath fast neutral yellow tints.

7.) 20,17kg. of 5-aminoTQ;sultobenzaldehydeare diazotized asusual with 6,9 kg. of sodium nitriteandcoupled at 0,590, with asodaalkaline solution Qt.25,41,1 g. ot ,1-psulfophenyhfianethyh5'Py1'azclone. There results a deep yellow colored solution, from which the dyestufi may be isolated by salting out. It forms when dry a light yellow powder which is already easily soluble in cold water and dyes wool in an acid bath fast pure yellow tints. V

8.) If in Example 1 are used instead of the 1-sulf0phenyl 5-py1aZol0ne3rcarboxylic acid 90 kg. of l-R-sulfoz naphthyl-3- inethyl 5pyrazolone, a very fast dyestufl is obtained dyeing brownish-yellow tints.

The dyestuff has probably the following formula: I l

'9;) 12,1 kg; ofn -aminobenzaldehyde or 11,2 of the anhydro, compound of-msodium salt.

0.) .46,9 kglqt lrchloro-5 an1inobenZalde' ture;

aininobenzaldehyde are diazotised as detliyl-o pyrazolone(of 61 per cent) At once the formation of the new azo dyestuil' takes place, the solution takes adeep yellow colour. The dyestuff may be precipitated by means or common salt from 1ts solution as yellow powder and dyes wool in an acid bath very pure yellow tints with a green hue of good fastness to alkali, steaming and sulph ,and of a very'good i'astness to wash; ing, fulling and ;water. By chroming it afterwards the dyeing beomes somewhat darker and then surpasses the well-knownniordantingyellow as well-as regards its green hueas also especially concerning the fastness to carbonization.

10.) If in Example 9, the pyrazolonederivative mentioned therein isjreplaced ,by

kg. of ,2L5 -dichloro itt sulfophenyl-5- pyrazolonerlrcarboxylic acid, ,a dyestufif is obtained which dyes very pure greenishyellow tints.

iHaving nouidescribed my inv 1 claim is:

AS11613 products the dyestufi's which dye cntion, what woolgreenish-yellow to reddishsyellow fast tints. and correspond; to theforn ula 'oHo.-'B.- N:i\T-;R%

wherein ER means .a- (benzene- 1 residue, which may 1361 substituted in ra ny W 21y, containing the;aldehydewgroup in 111TPQSltZl,O11,;1%ll1,Cl R nc-ans arylpyiiazolones their derivatives and substitution products forming greenish-yellowito reddish-yellow powders readily dissolvingi'n hot water,.dissolvingin concern trated sulfuric acid. with ,ayellowish-green to orange yellow colour andQcont-aining the freewaldehyde group, consequently showing the reactions characteristic for the said group, suchfor instance as the formation of bisulfite' compounds which are very readily soluble in cold water, and condensation with o-hydroxycarboxylic acids of the benzeneand naphthalene series to leucotriaryln1eth'ane -dyestufis.

#In testimony whereof, I afiix my signa- V KAR TH Ess.

Witnesses: i

AL'rAFJiE C. B. WYLns.

Then dry, it constitutes 

